A type of Tb 3+ Sensitized Eu 3+ Luminescent scintillation glass, its preparation method and application
By introducing Tb3+ ions as a sensitizer into scintillation glass, the red scintillation emission of Eu3+ is enhanced, solving the problems of complex and costly preparation of existing scintillation materials and realizing efficient X-ray imaging and detection applications.
Patent Information
- Application Number
- CN202611495987.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-09-24
- Publication Date
- 2026-11-03
AI Technical Summary
The X-ray excitation luminescence performance of existing Eu3+ doped scintillation glasses has not yet reached its optimal level. Traditional scintillation single crystals have problems such as complex preparation, high cost, and difficulty in large-size preparation. Moreover, the application needs of traditional scintillation materials in X-ray imaging, industrial non-destructive testing, and radiation detection have not been fully met.
A scintillation glass sensitized by Tb3+ to emit Eu3+ light was developed. By introducing Tb3+ ions into the glass as sensitizing ions, an energy transfer channel was constructed to enhance the red scintillation intensity of Eu3+. The glass was prepared using a high-temperature melting-quenching method, which simplifies the process and reduces costs.
It improves the scintillation intensity of Eu3+, achieves high transparency and physicochemical stability, is easy to fabricate in large sizes and process complex shapes, and is suitable for X-ray imaging, industrial non-destructive testing and radiation detection.
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Figure CN123026375A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of scintillation materials technology, and particularly to a Tb 3+ Sensitized Eu 3+ A red luminescent scintillation glass, its preparation method, and its applications are disclosed. The scintillation glass can be used in fields such as X-ray imaging, radiation detection, and industrial non-destructive testing. Background Technology
[0002] X-rays, with their strong penetrating power, are widely used in medical diagnosis, industrial non-destructive testing, security inspection, and materials structure analysis. Scintillation materials are key materials in X-ray imaging systems, absorbing the energy of incident X-rays and converting it into visible light signals that can be collected by photodetectors. Currently, commonly used scintillation materials mainly include Bi4Ge3O4. 12 Scintillation crystals such as BGO, CsI:Tl, and NaI:Tl are examples. Although scintillation crystals generally have high luminous efficiency, their preparation process is complex, costly, and they face challenges in large-size fabrication and limited processing shapes.
[0003] Compared to scintillation single crystals, scintillation glasses offer advantages such as tunable composition, simple fabrication process, lower cost, better optical uniformity, and ease of large-size fabrication and complex shape processing. They can also be further fabricated into scintillation fibers. Among these, fluoroborosilicate glasses exhibit good glass-forming ability and tunable composition. Appropriate amounts of SiO2 and Al2O3 are beneficial for improving the stability of the glass network structure. Simultaneously, introducing BaF2 into the glass system increases the glass density, enhances X-ray absorption, and, by adjusting the glass network structure and phonon energy, improves the luminescence performance of rare-earth ions.
[0004] Eu 3+ It has abundant 4f electron energy levels, 5 D0→ 7 The F2 transition produces a characteristic red emission at 612 nm, which matches well with the response band of commonly used photodetectors. Previous studies have reported that Eu... 3+ The X-ray integrated luminescence intensity of calcium gadolinium borosilicate glass is approximately 13% that of BGO crystals (see N. Wantana, E. Kaewnuam, B. Damdee, et al., Journal of Luminescence, 2018, 194: 75–81.). Eu 3+The X-ray excitation integrated intensity of boron aluminosilicate glass can reach 22.7% of that of BGO crystal, and the X-ray imaging spatial resolution can reach 14 lp / mm (see Y. Gong, L. Li, J. Chen, H. Guo., Materials, 2023, 16: 4711.). Eu 3+ The integrated scintillation intensity of gadolinium borogerate glass can reach approximately 32% of that of BGO crystal, indicating that Eu... 3+ Doped glasses have good potential for X-ray imaging applications (see N. Wantana, E. Kaewnuam, F. Khrongchaiyaphum, et al., Radiation Physics and Chemistry, 2026, 238: 113193.).
[0005] However, the existing Eu 3+ There is still room for improvement in the X-ray excitation luminescence performance of doped scintillation glasses. Improving Eu... 3+ Utilizing X-ray excitation energy efficiently is an important way to enhance its red scintillation emission. Tb 3+ It has abundant excitation energy levels in Eu 3+ / Tb 3+ In co-doped systems, the energy transfer process between rare earth ions can be used to regulate Eu. 3+ Its luminescent properties.
[0006] Therefore, it is necessary to develop a method that has good transparency and physicochemical stability, simple preparation process, low raw material cost, and can pass through Tb 3+ With Eu 3+ Energy transfer between Eu increases 3+ A novel glass material with red scintillation intensity is developed to meet the application requirements of high-performance, large-size, and easily processed scintillation materials in fields such as X-ray imaging, industrial non-destructive testing, and radiation detection. Summary of the Invention
[0007] The purpose of this invention is to provide a Tb for X-ray imaging. 3+ Sensitized Eu 3+ A luminescent scintillation glass and its preparation method. This glass features high transparency, high intensity of red scintillation emission, stable physicochemical properties, simple preparation process, low cost, and ease of fabrication in large sizes and complex shapes. It can be further fabricated into scintillation optical fibers, showing promising application prospects in X-ray imaging and radiation detection.
[0008] The technical solution adopted in this invention is: a scintillation glass for X-ray imaging, wherein the glass composition has the following molar percentages: 20-50 mol% BaF2, 5-30 mol% SiO2, 10-40 mol% B2O3, 5-30 mol% Al2O3, 0.1-7 mol% Eu2O3, and 1-3 mol% Tb4O7, and the sum of the molar percentages of each component is 100%.
[0009] Furthermore, the glass composition has the following molar percentages: 30-40 mol% BaF2, 15-25 mol% SiO2, 25-35 mol% B2O3, 8-12 mol% Al2O3, 3-7 mol% Eu2O3, and 1-3 mol% Tb4O7.
[0010] Furthermore, the glass composition has the following molar percentages: 35 mol% BaF2, 20 mol% SiO2, 28.25 mol% B2O3, 10 mol% Al2O3, 5 mol% Eu2O3, and 1.75 mol% Tb4O7.
[0011] The Eu2O3 is used to introduce Eu into the glass. 3+ Luminescent ions, Eu 3+ As a red scintillation emission center, it generates Eu under X-ray excitation. 3+ The characteristic emission is predominantly red light. The Tb4O7 is used to introduce Tb into the glass. 3+ Ions, Tb 3+ Ions, as sensitizing ions, enhance Eu 3+ The red scintillating luminescence intensity is determined. The BaF2 is used to increase the glass's density and X-ray absorption capacity, while also adjusting the glass network structure and phonon energy, which is beneficial for improving the luminescence performance of rare earth ions. The scintillating glass is transparent glass, and its form can be one of a block scintillator, a scintillating sheet, or a scintillating fiber.
[0012] The present invention also provides a method for preparing the above-mentioned red scintillation glass for X-ray imaging, comprising the following steps: ① Based on the above scintillation glass composition and molar percentage, calculate the mass of each glass component, accurately weigh each raw material, the B2O3 can be introduced by B2O3 or H3BO3, and Al2O3 can be introduced by Al(OH)3 or Al2O3; grind the weighed raw materials in an agate mortar and mix them evenly to form a mixture. ② Take the mixture and put it into a high-temperature furnace. Raise the temperature from room temperature to 1000~1300℃ and melt for 10-60 minutes. Take out the resulting glass liquid and quickly pour it onto an aluminum plate to obtain a transparent glass sample. ③ Transfer the obtained glass sample to a muffle furnace at 470~500℃ for annealing. After holding at this temperature for 3~5 hours, allow it to cool naturally to room temperature. Once completely cooled, remove the glass.
[0013] Furthermore, in step ②, the high-temperature furnace is a silicon carbide rod electric furnace, which is heated from room temperature to 1200°C and melted for 10 minutes; in step ③, the annealing temperature is 470°C and the holding time is 3 hours.
[0014] The present invention also provides the above-mentioned Tb 3+ Sensitized Eu 3+ Applications of luminescent scintillation glass in X-ray imaging, industrial non-destructive testing, or radiation detection.
[0015] Compared with the prior art, the beneficial technical effects of the present invention are as follows: This invention discloses a Tb for X-ray imaging 3+ Sensitized Eu 3+ Red luminescent scintillation glass. The scintillation glass is prepared by a high-temperature melting-quenching method, which has the advantages of low raw material cost, simple preparation process and good glass formation performance. It can avoid the problems of long growth cycle, high preparation cost and difficulty in large-size preparation of traditional scintillation single crystals.
[0016] This invention uses Eu³ + As a red flashing luminescent center, the glass can produce a light emission with Eu under X-ray excitation. 3+ The characteristic emission spectrum is predominantly red scintillation. This is achieved by introducing Tb... 3+ As a sensitizing ion, construct Tb 3+ To Eu 3+ The energy transfer channels, thereby enhancing Eu 3+ The intensity of the scintillation emission. In embodiments of the present invention, compared with undoped Tb... 3+ Eu 3+ Compared to single-doped glass, Tb 3+ / Eu 3+ Eu in co-doped glass 3+ The integrated scintillation luminescence intensity increased by approximately 1.55 times, indicating that Tb 3+ For Eu 3+ It has a significant sensitizing effect.
[0017] The scintillation glass prepared by this invention possesses good transparency, physicochemical stability, and scintillation luminescence performance. It also features a wide range of compositional control, short preparation cycle, ease of large-scale fabrication, and convenient processing into various shapes. Furthermore, the scintillation glass can be further fabricated into bulk scintillators, scintillation sheets, or scintillation fibers, showing promising application prospects in fields such as X-ray imaging, industrial non-destructive testing, radiation detection, and security inspection. Attached Figure Description
[0018] Figure 1 This is a comparison of the X-ray excitation emission spectra of Example 1#, Comparative Example 1#, and a commercial BGO scintillation crystal in this invention; Figure 2 The image is obtained by X-ray imaging of a Type 39b line pair card (containing different line pair numbers of 3, 4, 5, 10, 20, and 30 lp / mm) using Embodiment 1# of the present invention; Figure 3 The image is obtained by X-ray imaging of the spring inside the capsule using Example 1# of the present invention. Detailed Implementation
[0019] The specific technical solutions in the embodiments of the present invention will be described below. The parts described below are not all examples of the present invention. Other examples that are not inventive and are based on the present invention are all within the protection scope of the present invention.
[0020] The present invention describes Tb for X-ray imaging 3+ Sensitized Eu 3+ The glass composition of the specific implementation of the scintillating glass is as follows: Table 1: Glass composition of Examples 1-15 and Comparative Example 1 Example 1#: The preparation process of Example 1 is as follows: Table 2: Composition of matrix glass in Example 1 First, according to the matrix glass composition shown in Table 2, a total of 20g of glass raw materials was weighed. The raw materials consisted of 7.939g BaF2, 1.555g SiO2, 4.519g H3BO3, 2.018g Al(OH)3, 2.276g Eu2O3, and 1.693g Tb4O7. The B2O3 in the glass composition was introduced from H3BO3, and the Al2O3 was introduced from Al(OH)3. The weighed raw materials were then mixed evenly in an agate mortar to obtain a glass mixture. Subsequently, the glass mixture was placed in a corundum crucible and then placed in a silicon carbide electric furnace, where it was melted at 1200℃ for 10 minutes to ensure complete melting. The resulting molten glass was quickly poured onto an aluminum plate and pressed into glass sheets. The resulting glass was transferred to an annealing furnace at 470℃ for 3 hours, cooled to room temperature in the furnace, and then removed to obtain transparent Eu2O3. 3+ / Tb 3+ Co-doped scintillation glass. Under ultraviolet light excitation, the prepared glass sample exhibits strong red fluorescence. Furthermore, as... Figure 1As shown, under X-ray excitation, the scintillation glass of Example 1# can produce Eu. 3+ The characteristic red scintillation emission has an integrated luminescence intensity that is 42.7% of that of commercial BGO scintillation crystals. Using the prepared Example 1# scintillation glass as the scintillation conversion material, X-ray imaging was performed on a Type 39b wire pair card and a capsule containing an internal metal spring. Figure 2 As shown, the X-ray imaging results of the line pair cards obtained using the glass of Example 1# can clearly distinguish line pair structures with different spacings (including 3, 4, 5, 10, 20, and 30 lp / mm), indicating that the glass has good spatial resolution. Figure 3 As shown, the internal metal spring structure of the capsule can be clearly displayed, indicating that the scintillation glass has good X-ray imaging capabilities.
[0021] Comparative Example 1#: The preparation process of Comparative Example 1 is as follows: Table 3: Composition of matrix glass in Comparative Example 1 First, according to the matrix glass composition shown in Table 3, a total of 20 g of glass raw materials was weighed. The raw materials consisted of 8.542 g BaF2, 1.673 g SiO2, 5.164 g H3BO3, 2.172 g Al(OH)3, and 2.44 g Eu2O3, with no Tb4O7 added. The B2O3 in the glass composition was introduced from H3BO3, and the Al2O3 was introduced from Al(OH)3. The weighed raw materials were then mixed evenly in an agate mortar to obtain a glass mixture. Subsequently, the glass mixture was placed in a corundum crucible and then placed in a silicon carbide electric furnace, where it was held at 1200°C for 10 minutes to ensure complete melting. The resulting molten glass was quickly poured onto an aluminum plate and pressed into glass sheets. The resulting glass was transferred to an annealing furnace at 470°C for 3 hours, cooled to room temperature in the furnace, and then removed to obtain Eu2O3. 3+ Single-doped transparent scintillation glass. Under ultraviolet light excitation, the prepared glass sample exhibits strong red fluorescence. For example... Figure 1 As shown, under X-ray excitation, Comparative Example 1 glass exhibits Eu... 3+ It exhibits a characteristic red flashing light. Compared to the Eu prepared in Example 1... 3 + / Tb 3+ Compared to co-doped glass, Comparative Example 1# Eu 3+ The flickering luminescence intensity is significantly reduced. This indicates that Tb 3+ The introduction of ions can effectively enhance Eu 3+ It flashes and glows.
[0022] Example 2#: The preparation process of Example 2 is as follows: Table 4: Composition of matrix glass in Example 2 First, according to the matrix glass composition shown in Table 4, a total of 20 g of glass raw materials was weighed. The raw materials consisted of 9.588 g BaF2, 1.878 g SiO2, 3.263 g B2O3, 1.593 g Al2O3, 1.925 g Eu2O3, and 1.752 g Tb4O7. The weighed raw materials were then mixed evenly in an agate mortar to obtain a glass mixture. Subsequently, the glass mixture was placed in a corundum crucible and then placed in a silicon carbide electric furnace, where it was melted at 1200°C for 10 minutes to ensure complete melting. The resulting molten glass was quickly poured onto an aluminum plate and pressed into glass sheets. The resulting glass was transferred to an annealing furnace at 470°C for 3 hours, cooled to room temperature in the furnace, and then removed to obtain transparent Eu2O3. 3+ / Tb 3+ Co-doped scintillation glass. Under ultraviolet light excitation, the prepared glass sample exhibits red fluorescence. Under X-ray excitation, the prepared glass exhibits Eu fluorescence. 3+ Its characteristic red flashing light. Example 3#: The preparation process of Example 3 is as follows: Table 5: Composition of matrix glass in Example 3 First, according to the matrix glass composition shown in Table 5, a total of 20 g of glass raw materials was weighed. The raw materials consisted of 10.297 g BaF2, 0.706 g SiO2, 3.341 g H3BO3, 1.833 g Al(OH)3, 2.067 g Eu2O3, and 1.757 g Tb4O7. The B2O3 in the glass composition was introduced from H3BO3, and the Al2O3 was introduced from Al(OH)3. The weighed raw materials were then mixed evenly in an agate mortar to obtain a glass mixture. Subsequently, the glass mixture was placed in a corundum crucible and then placed in a silicon carbide electric furnace, where it was held at 1100°C for 60 minutes to ensure complete melting. The resulting molten glass was quickly poured onto an aluminum plate and pressed into glass sheets. The resulting glass was transferred to an annealing furnace at 480°C for 3 hours, cooled to room temperature in the furnace, and then removed to obtain transparent Eu2O3. 3+ / Tb 3+ Co-doped scintillation glasses. Under ultraviolet light excitation, the prepared glass samples exhibit red fluorescence. Under X-ray excitation, all prepared glasses show Eu fluorescence. 3+ Its characteristic is a red flashing light.
[0023] Example 4#: The preparation process of Example 4 is as follows: Table 6: Composition of matrix glass in Example 4 First, according to the matrix glass composition shown in Table 6, a total of 20 g of glass raw materials was weighed. The raw materials consisted of 9.235 g BaF2, 0.352 g SiO2, 4.777 g H3BO3, 1.826 g Al(OH)3, 2.060 g Eu2O3, and 1.750 g Tb4O7. The B2O3 in the glass composition was introduced from H3BO3, and the Al2O3 was introduced from Al(OH)3. The weighed raw materials were then mixed evenly in an agate mortar to obtain a glass mixture. Subsequently, the glass mixture was placed in a corundum crucible and then placed in a silicon carbide electric furnace, where it was held at 1300°C for 30 minutes to ensure complete melting. The resulting molten glass was quickly poured onto an aluminum plate and pressed into glass sheets. The resulting glass was transferred to an annealing furnace at 500°C for 5 hours, cooled to room temperature in the furnace, and then removed to obtain transparent Eu2O3. 3+ / Tb 3+ Co-doped scintillation glasses. Under ultraviolet light excitation, the prepared glass samples exhibit red fluorescence. Under X-ray excitation, all prepared glasses show Eu fluorescence. 3+ Its characteristic is a red flashing light.
[0024] Example 5#: The preparation process of Example 5 is as follows: Table 7: Composition of the matrix glass in Example 5 First, according to the matrix glass composition shown in Table 7, a total of 20 g of glass raw materials was weighed. The raw materials consisted of 8.193 g BaF2, 2.407 g SiO2, 2.972 g H3BO3, 2.083 g Al(OH)3, 1.997 g Eu2O3, and 1.997 g Tb4O7. The B2O3 in the glass composition was introduced from H3BO3, and the Al2O3 was introduced from Al(OH)3. The weighed raw materials were then mixed evenly in an agate mortar to obtain a glass mixture. Subsequently, the glass mixture was placed in a corundum crucible and then placed in a silicon carbide electric furnace, where it was held at 1300°C for 30 minutes to ensure complete melting. The resulting molten glass was quickly poured onto an aluminum plate and pressed into glass sheets. The resulting glass was transferred to an annealing furnace at 500°C for 4 hours, cooled to room temperature in the furnace, and then removed to obtain transparent Eu2O3. 3+ / Tb 3+ Co-doped scintillation glasses. Under ultraviolet light excitation, the prepared glass samples exhibit red fluorescence. Under X-ray excitation, all prepared glasses show Eu fluorescence. 3+ Its characteristic is a red flashing light.
[0025] Example 6#: The preparation process of Example 6 is as follows: Table 8: Composition of the matrix glass in Example 6 First, according to the matrix glass composition shown in Table 8, a total of 20 g of glass raw materials was weighed. The raw materials consisted of 10.225 g BaF2, 2.336 g SiO2, 1.603 g H3BO3, 1.617 g Al(OH)3, 2.281 g Eu2O3, and 1.938 g Tb4O7. The B2O3 in the glass composition was introduced from H3BO3, and the Al2O3 was introduced from Al(OH)3. The weighed raw materials were then mixed evenly in an agate mortar to obtain a glass mixture. Subsequently, the glass mixture was placed in a corundum crucible and then placed in a silicon carbide electric furnace, where it was melted at 1200 °C for 60 min to ensure complete melting. The resulting molten glass was quickly poured onto an aluminum plate and pressed into glass sheets. The resulting glass was transferred to an annealing furnace at 480 °C for 5 hours, cooled to room temperature in the furnace, and then removed to obtain transparent Eu2O3. 3+ / Tb 3+ Co-doped scintillation glasses. Under ultraviolet light excitation, the prepared glass samples exhibit red fluorescence. Under X-ray excitation, all prepared glasses show Eu fluorescence. 3+ Its characteristic is a red flashing light.
[0026] Example 7#: The preparation process of Example 7 is as follows: Table 9: Composition of the matrix glass in Example 7 First, according to the matrix glass composition shown in Table 9, a total of 20 g of glass raw materials was weighed. The raw materials consisted of 6.538 g BaF2, 0.747 g SiO2, 6.148 g H3BO3, 2.521 g Al(OH)3, 2.187 g Eu2O3, and 1.859 g Tb4O7. The B2O3 in the glass composition was introduced from H3BO3, and the Al2O3 was introduced from Al(OH)3. The weighed raw materials were then mixed evenly in an agate mortar to obtain a glass mixture. Subsequently, the glass mixture was placed in a corundum crucible and then placed in a silicon carbide electric furnace, where it was held at 1000°C for 30 minutes to ensure complete melting. The resulting molten glass was quickly poured onto an aluminum plate and pressed into glass sheets. The resulting glass was transferred to an annealing furnace at 500°C for 3 hours, cooled to room temperature in the furnace, and then removed to obtain transparent Eu2O3. 3+ / Tb 3+Co-doped scintillation glasses. Under ultraviolet light excitation, the prepared glass samples exhibit red fluorescence. Under X-ray excitation, all prepared glasses show Eu fluorescence. 3+ Its characteristic is a red flashing light.
[0027] Example 8#: The preparation process of Example 8 is as follows: Table 10: Composition of the matrix glass in Example 8 First, according to the matrix glass composition shown in Table 10, a total of 20 g of glass raw materials was weighed. The raw materials consisted of 8.927 g BaF2, 1.530 g SiO2, 4.407 g H3BO3, 0.993 g Al(OH)3, 2.240 g Eu2O3, and 1.903 g Tb4O7. The B2O3 in the glass composition was introduced from H3BO3, and the Al2O3 was introduced from Al(OH)3. The weighed raw materials were then mixed evenly in an agate mortar to obtain a glass mixture. Subsequently, the glass mixture was placed in a corundum crucible and then placed in a silicon carbide electric furnace, where it was held at 1100°C for 60 minutes to ensure complete melting. The resulting molten glass was quickly poured onto an aluminum plate and pressed into glass sheets. The resulting glass was transferred to an annealing furnace at 500°C for 4 hours, cooled to room temperature in the furnace, and then removed to obtain transparent Eu2O3. 3+ / Tb 3+ Co-doped scintillation glasses. Under ultraviolet light excitation, the prepared glass samples exhibit red fluorescence. Under X-ray excitation, all prepared glasses show Eu fluorescence. 3+ Its characteristic is a red flashing light.
[0028] Example 9#: The preparation process of Example 9 is as follows: Table 11: Composition of the matrix glass in Example 9 First, according to the matrix glass composition shown in Table 11, a total of 20 g of glass raw materials was weighed. The raw materials consisted of 6.322 g BaF2, 0.722 g SiO2, 3.419 g H3BO3, 5.625 g Al(OH)3, 2.115 g Eu2O3, and 1.797 g Tb4O7. The B2O3 in the glass composition was introduced from H3BO3, and the Al2O3 was introduced from Al(OH)3. The weighed raw materials were then mixed evenly in an agate mortar to obtain a glass mixture. Subsequently, the glass mixture was placed in a corundum crucible and then placed in a silicon carbide electric furnace, where it was held at 1300°C for 10 minutes to ensure complete melting. The resulting molten glass was quickly poured onto an aluminum plate and pressed into glass sheets. The resulting glass was transferred to an annealing furnace at 500°C for 4 hours, cooled to room temperature in the furnace, and then removed to obtain transparent Eu2O3. 3+ / Tb 3+ Co-doped scintillation glasses. Under ultraviolet light excitation, the prepared glass samples exhibit red fluorescence. Under X-ray excitation, all prepared glasses show Eu fluorescence. 3+ Its characteristic is a red flashing light.
[0029] Example 10#: The preparation process of Example 10 is as follows: Table 12: Composition of the matrix glass in Example 10 First, according to the matrix glass composition shown in Table 12, a total of 20 g of glass raw materials was weighed. The raw materials consisted of 8.846 g BaF2, 1.732 g SiO2, 6.044 g H3BO3, 2.249 g Al(OH)3, 0.051 g Eu2O3, and 1.078 g Tb4O7. The B2O3 in the glass composition was introduced from H3BO3, and the Al2O3 was introduced from Al(OH)3. The weighed raw materials were then mixed evenly in an agate mortar to obtain a glass mixture. Subsequently, the glass mixture was placed in a corundum crucible and then placed in a silicon carbide electric furnace, where it was melted at 1200°C for 10 minutes to ensure complete melting. The resulting molten glass was quickly poured onto an aluminum plate and pressed into glass sheets. The resulting glass was transferred to an annealing furnace at 470°C for 3 hours, cooled to room temperature in the furnace, and then removed to obtain transparent Eu2O3. 3+ / Tb 3+ Co-doped scintillation glasses. Under ultraviolet light excitation, the prepared glass samples exhibit red fluorescence. Under X-ray excitation, all prepared glasses show Eu fluorescence. 3+ Its characteristic is a red flashing light.
[0030] Example 11#: The preparation process of Example 11 is as follows: Table 13: Composition of matrix glass in Example 11 First, according to the matrix glass composition shown in Table 13, a total of 20 g of glass raw materials was weighed. The raw materials consisted of 6.755 g BaF2, 1.158 g SiO2, 5.559 g H3BO3, 2.404 g Al(OH)3, 3.164 g Eu2O3, and 0.960 g Tb4O7. The B2O3 in the glass composition was introduced from H3BO3, and the Al2O3 was introduced from Al(OH)3. The weighed raw materials were then mixed evenly in an agate mortar to obtain a glass mixture. Subsequently, the glass mixture was placed in a corundum crucible and then placed in a silicon carbide electric furnace, where it was held at 1300°C for 30 minutes to ensure complete melting. The resulting molten glass was quickly poured onto an aluminum plate and pressed into glass sheets. The resulting glass was transferred to an annealing furnace at 500°C for 3 hours, cooled to room temperature in the furnace, and then removed to obtain transparent Eu2O3. 3+ / Tb 3+ Co-doped scintillation glasses. Under ultraviolet light excitation, the prepared glass samples exhibit red fluorescence. Under X-ray excitation, all prepared glasses show Eu fluorescence. 3+ Its characteristic is a red flashing light.
[0031] Example 12#: The preparation process of Example 12 is as follows: Table 14: Composition of matrix glass in Example 12 First, according to the matrix glass composition shown in Table 14, a total of 20 g of glass raw materials was weighed. The raw materials consisted of 7.025 g BaF2, 2.006 g SiO2, 4.955 g H3BO3, 1.667 g Al(OH)3, 2.350 g Eu2O3, and 1.997 g Tb4O7. The B2O3 in the glass composition was introduced from H3BO3, and the Al2O3 was introduced from Al(OH)3. The weighed raw materials were then mixed evenly in an agate mortar to obtain a glass mixture. Subsequently, the glass mixture was placed in a corundum crucible and then placed in a silicon carbide electric furnace, where it was melted at 1200°C for 10 minutes to ensure complete melting. The resulting molten glass was quickly poured onto an aluminum plate and pressed into glass sheets. The resulting glass was transferred to an annealing furnace at 470°C for 3 hours, cooled to room temperature in the furnace, and then removed to obtain transparent Eu2O3. 3+ / Tb 3+ Co-doped scintillation glasses. Under ultraviolet light excitation, the prepared glass samples exhibit red fluorescence. Under X-ray excitation, all prepared glasses show Eu fluorescence. 3+Its characteristic is a red flashing light.
[0032] Example 13#: The preparation process of Example 13 is as follows: Table 15: Composition of the matrix glass in Example 13 First, according to the matrix glass composition shown in Table 15, a total of 20 g of glass raw materials was weighed. The raw materials consisted of 8.914 g BaF2, 1.146 g SiO2, 4.715 g H3BO3, 1.983 g Al(OH)3, 1.342 g Eu2O3, and 1.901 g Tb4O7. The B2O3 in the glass composition was introduced from H3BO3, and the Al2O3 was introduced from Al(OH)3. The weighed raw materials were then mixed evenly in an agate mortar to obtain a glass mixture. Subsequently, the glass mixture was placed in a corundum crucible and then placed in a silicon carbide electric furnace, where it was melted at 1200°C for 10 minutes to ensure complete melting. The resulting molten glass was quickly poured onto an aluminum plate and pressed into glass sheets. The resulting glass was transferred to an annealing furnace at 470°C for 3 hours, cooled to room temperature in the furnace, and then removed to obtain transparent Eu glass. 3+ / Tb 3+ Co-doped scintillation glasses. Under ultraviolet light excitation, the prepared glass samples exhibit red fluorescence. Under X-ray excitation, all prepared glasses show Eu fluorescence. 3+ Its characteristic is a red flashing light.
[0033] Example 14#: The preparation process of Example 14 is as follows: Table 16: Composition of the matrix glass in Example 14 First, according to the matrix glass composition shown in Table 16, a total of 20 g of glass raw materials was weighed. The raw materials consisted of 4.937 g BaF2, 2.538 g SiO2, 5.746 g H3BO3, 2.197 g Al(OH)3, 2.477 g Eu2O3, and 2.105 g Tb4O7. The B2O3 in the glass composition was introduced from H3BO3, and the Al2O3 was introduced from Al(OH)3. The weighed raw materials were then mixed evenly in an agate mortar to obtain a glass mixture. Subsequently, the glass mixture was placed in a corundum crucible and then placed in a silicon carbide electric furnace, where it was held at 1300°C for 10 minutes to ensure complete melting. The resulting molten glass was quickly poured onto an aluminum plate and pressed into glass sheets. The resulting glass was transferred to an annealing furnace at 480°C for 4 hours, cooled to room temperature in the furnace, and then removed to obtain transparent Eu2O3. 3+ / Tb 3+Co-doped scintillation glasses. Under ultraviolet light excitation, the prepared glass samples exhibit red fluorescence. Under X-ray excitation, all prepared glasses show Eu fluorescence. 3+ Its characteristic is a red flashing light.
[0034] Example 15#: The preparation process of Example 15 is as follows: Table 17: Composition of the matrix glass in Example 15 First, according to the matrix glass composition shown in Table 17, a total of 20 g of glass raw materials was weighed. The raw materials consisted of 7.351 g BaF2, 1.439 g SiO2, 3.703 g H3BO3, 1.869 g Al(OH)3, 2.951 g Eu2O3, and 2.687 g Tb4O7. The B2O3 in the glass composition was introduced from H3BO3, and the Al2O3 was introduced from Al(OH)3. The weighed raw materials were then mixed evenly in an agate mortar to obtain a glass mixture. Subsequently, the glass mixture was placed in a corundum crucible and then placed in a silicon carbide electric furnace, where it was melted at 1200°C for 10 minutes to ensure complete melting. The resulting molten glass was quickly poured onto an aluminum plate and pressed into glass sheets. The resulting glass was transferred to an annealing furnace at 470°C for 3 hours, cooled to room temperature in the furnace, and then removed to obtain transparent Eu2O3. 3+ / Tb 3+ Co-doped scintillation glasses. Under ultraviolet light excitation, the prepared glass samples exhibit red fluorescence. Under X-ray excitation, all prepared glasses show Eu fluorescence. 3+ Its characteristic is a red flashing light.
[0035] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.
Claims
1. A type of Tb 3+ Sensitized Eu 3+ The luminescent, shimmering glass is characterized by, The glass composition has the following molar percentages: 20-50 mol% BaF2, 5-30 mol% SiO2, 10-40 mol% B2O3, 5-30 mol% Al2O3, 0.1-7 mol% Eu2O3, and 1-3 mol% Tb4O7, with the sum of the molar percentages of each component being 100%; the Eu2O3 is used to introduce Eu into the glass. 3+ As a light-emitting center, the Tb4O7 is used to introduce Tb into the glass. 3+ As a sensitizing ion, the Tb 3+ Used to transfer the absorbed excitation energy to Eu 3+ To enhance Eu 3+ Its red glow is flashing.
2. A Tb as described in claim 1 3+ Sensitized Eu 3+ The luminescent, shimmering glass is characterized by, Based on the molar percentage of the glass composition, it includes: 30~40 mol% BaF2, 15~25 mol% SiO2, 25~35 mol% B2O3, 8~12 mol% Al2O3, 3~7 mol% Eu2O3, and 1~3 mol% Tb4O7, with the sum of the molar percentages of each component being 100%.
3. A Tb as described in claim 2 3+ Sensitized Eu 3+ The luminescent, shimmering glass is characterized by, The glass composition, by molar percentage, includes: 35 mol% BaF2, 20 mol% SiO2, 28.25 mol% B2O3, 10 mol% Al2O3, 5 mol% Eu2O3, and 1.75 mol% Tb4O7.
4. A Tb as described in any one of claims 1 to 3 3+ Sensitized Eu 3+ The luminescent, shimmering glass is characterized by, The scintillating glass is transparent glass, and the scintillating glass is in the form of a block scintillator, a scintillating sheet, or a scintillating fiber.
5. A Tb according to any one of claims 1 to 3 3+ Sensitized Eu 3+ A method for preparing luminescent scintillation glass, characterized in that, Includes the following steps: ① Calculate the mass of each glass component according to the composition and molar percentage of the scintillation glass, accurately weigh each raw material, wherein the B2O3 is introduced by B2O3 or H3BO3, and the Al2O3 is introduced by Al(OH)3 or Al2O3; grind the weighed raw materials in an agate mortar and mix them evenly to form a mixture; ② Take the mixture and put it into a high-temperature furnace, raise the temperature from room temperature to 1000~1300 ℃, and melt it for 10-60 minutes; take out the resulting glass liquid and quickly pour it onto an aluminum plate to obtain a transparent glass sample; ③ Transfer the obtained glass sample to a muffle furnace at 470~500 ℃ for annealing. After holding at this temperature for 3~5 hours, allow it to cool naturally to room temperature in the furnace. Once completely cooled, remove the glass.
6. A Tb as described in claim 5 3+ Sensitized Eu 3+ A method for preparing luminescent scintillation glass, characterized in that, In step ②, the high-temperature furnace is a silicon carbide rod electric furnace, which is heated from room temperature to 1200°C and melted for 10 minutes; in step ③, the annealing temperature is 470°C and the holding time is 3 hours.
7. A Tb according to any one of claims 1 to 3 3+ Sensitized Eu 3+ Applications of luminescent scintillation glass in X-ray imaging, industrial non-destructive testing, or radiation detection.